Phosphoric acid esters and pesticidal preparations containing them

ABSTRACT

THIS INVENTION RELATES TO A COMPOUND OF THE FORMULA   R1-O-P(=X)(-O-R2)-O-CH=C(-R2)-CO-R4   IN WHICH R1 AND R2 ARE INDENTICAL OR DIFFERENT LOWER ALKYL GROUPS, X IS AN OXYGEN OR A SULPHUR ATOM, R3 REPRESENTS A HYDROGEN ATOMS, AN ALKYL GROUP OR A HALOGEN ATOM AND R4 REPRESENTS A LOWER ALKOXY GROUP, AN ALKYL GROUP OR AN UNSUBSTITUTED OR SUBSTITUTED ARYL GROUP. THE COMPOUNDS ARE USEFUL FOR COMBATING INSECTS AND ACARIDS.

United States Patent 3,781,426 PHOSPHORIC ACID ESTERS AND PESTICIDALPREPARATIONS CONTAINING THEM Ernst Beriger, Allschwil, and LadislausPinter, Basel, Switzerland, assignors to Ciba-Geigy AG, Basel,Switzerland No Drawing. Original application July 24 1967, Ser. No.655,289, now Patent No. 3,594,454. Divided and this application Mar. 9,1971, Ser. No. 122,501 Claims priority application Switzerland, July 25,1966, 10,735/ 66 Int. Cl. A01n 9/36 US. Cl. 424-212 10 Claims ABSTRACTOF THE DISCLOSURE This invention relates to a compound of the formula inwhich R and R are identical or different lower alkyl groups, X is anoxygen or a sulphur atom, R represents a hydrogen atom, an alkyl groupor a halogen atom and R represents a lower alkoxy group, an alkyl groupor an unsubstituted or substituted aryl group. The compounds are usefulfor combating insects and acarids.

CROSS-REFERENCE TO RELATED APPLICATIONS This is a division ofapplication Ser. No. 655,289, filed July 24, 1967, now US. Pat. No.3,594,454.

The present invention relates to phosphoric acid esters and pesticidalpreparations, especially preparations for combating harmful insects andsimilar pests, containing the phosphoric acid esters as activeingredient.

The present invention provides phosphoric acid ester of the generalformula R: (I) in which R and R are identical or different lower alkylgroups, X represents an oxygen or sulphur atom, R is a hydrogen atom, alower alkyl group or a halogen atom and R stands for a lower alkoxy oralkyl group or an unsubstituted or substituted aryl group.

The present invention also provides pesticidal preparations, preferablypreparations for combating harmful insects, which comprises as activeingredient a compound of the general formula given above, together witha suitable carrier.

As mentioned above, R may be a lower alkoxy group, for example, methoxy,ethoxy, propoxy, isopropoxy or butoxy, or a lower alkyl group, forexample, methyl, ethyl, propyl, butyl or an unsubstituted or substitutedaryl group. The aryl group-which is preferably phenyl-may contain, assubstituents, halogen atoms, nitro groups, cyano groups, thiocyanogroups, trifluoromethyl groups and/or alkyl or alkoxy groups. Especiallyfavorable properties are found in those compounds of the General FormulaI in which R R and R have the above meanings and R represents a loweralkyl or alkoxy group, preferably the methyl or methoxy group. In thisconnection, compounds that are especially valuable are those in which Rrepresents methyl and X represents oxygen. The new phosphoric acidesters of the Formula I kill a variety of insects, for example,Orthoptera (crickets, locusts, cockroaches), Coleoptera (corn weavil,bacon beetle, meal beetle), Diptera (flies, midges), Homoptera (aphids),Aphaniph tera (fleas), Hymnoptera (ants), Lepidoptera (Prodenia,Limantria), and various other types of insects. Moreover,

3,781,426 Patented Dec. 25, 1973 "ice in which R and K, have the abovemeanings and Me stands for an alkali metal atom, for example, sodium orpotassiumwith a phosphoric or triophosphoric acid ester halide of theformula i -Ha wherein R R and X have the above meanings and Halrepresents a halogen atom.

The reaction may be carried out in a solvent, for example, in benzene,xylene or dioxane. Many of the esters manufactured in this manner can bepurified by distillation under a high vacuum.

Phosphoric acid esters of the formula in which R to K, have the abovemeaningsare also accessible by reacting a phosphite of the formula inwhich R, and R have the above meanings and R represents a lower alkylradical-with an lit-halogenated a-formylcarbonyl compound of the formulain which Hal stands for halogen, preferably chlorine or bromine, and Rand R have the above meanings.

The forms in which the new preparations are applied vary according tothe purpose for which they are to be used.

In order to manufacture spray solutions of the phosphoric acid esters ofthe General Formula I there may be used, for example, petroleumfractions having a high to medium boiling range, for example, diesel oilor kerosene, coal tar oil and oils of vegetable or animal origin andalso hydrocarbons, for example, alkylated naphthalenes,tetrahydronaphthalene, if desired with the use of xylene mixtures,cyclohexanols or ketones, or chlorinated hydrocarbons, for example,trichlorethane or tetrachlorethane trichloroethylene or triortetrachlorobenzenes. It is advantageous to use organic solvents thatboil above C.

It is especially advantageous to prepare aqueous forms of thepreparation from emulsion concentrates, pastes or wettable spray powdersby the addition of water. Suitable emulsifiers or dispersants arenonionic products, for example condensation products of aliphaticalcohols, amines or carboxylic acids containing a long-chain hydrocarbonresidue having about 10 to 20 carbon atoms with ethylene oxide, forexample, the condensation product of octadecyl alcohol with 25 to 30mols of ethylene oxide, or of soybean fatty acid with 30 mols ofethylene oxide, or of commercial oleylamine with 15 mols of ethyleneoxide or of dodecylmercaptan with 12 mols of ethylene oxide. Amongst thesuitable anionic emulsifiers there may be mentioned especially: thesodium salt of the dodecylalcohol sulphuric acid ester or ofdodecylbenzenesulphonic acid, the potassium or triethanolamine salt ofoleic acid or of abietic acid or of mixtures of these two acids,'or thesodium salt of a petroleumsulphonic acid. Suitable cationic dispersantsare quaternary ammonium compounds, for example, cetyl pyridinium bromideor dihydroxyethylbenzyl dodecyl ammonium chloride.

The following examples illustrate the invention, the parts being partsby Weight, except when otherwise stated.

EXAMPLE 1 (A) 145 parts of the sodium salt of oxymethylenepropionic acidethyl ester are suspended in 600 parts by volume of absolute benzeneand, while stirring and cool ing with ice, 165 g. ofdiethylchlorophosphate are added drop by drop during 30 minutes. Thebatch is allowed to react further overnight at room temperature, is thenwashed with 200 parts by volume of water and 2X50 parts by volume ofsaturated sodium bicarbonate solution, the benzolic solution is driedover sodium sulphate and the benzene is evaporated under vacuum. Theresidue (151 parts) is distilled under a high vacuum, to yield thephosphoric acid ester of the formula (CzHrO)aP0-CH=-COOC2H5 boiling at118l2l C., under 0.08 mm. Hg pressure.

In an identical manner, the following phosphoric acid esters areobtained:

EXAMPLE 2 8 grams of the phosphoric acid ester of Example 1 (Compound a)are mixed with 4 g. of Toximul Q (a mixture of a nonionic and an ionicemulsifier consisting of a condensation product of an alkylphenol with10 to 20 mols of ethylene oxide and calcium dodecylbenzenesulphonate),and the whole is made up to 20 g. by adding xylene. In this manner anemulsion concentrate of 40% strength is obtained, which can be dilutedwith water in any desired proportion.

EXAMPLE 3 Activity against flies (M usca dam'estica) Aqueous dilution(0.1%) of 20% emulsion concentrates from the compound of the Formula Hand the compound of Example 1(a) is prepared, and it is observed whenusing Compound II that the activity drops after one week by 94%, andafter 2 weeks by 99%, whereas when using the compound of Example 1, nodrop in activity is observed after one week and after 2 weeks a drop ofonly 30% IB.P. 105-110 0., under 0.02 mm.

Hg. pressure.

Example 4 When '62 to 125 g. per hectare of the compound of Example 1(a)are applied, it proves most eflective against German cockroach, Americancockroach, Russian cockroach, meal' beetle, bacon beetle, blood Worm,house cricket and the ant. In order to achieve an equivalent efiect withCompound II, at least twice the amount thereof was needed, that is tosay 250 g. of active substance per hectare, had to be used.

BP. (0.03 mm. Hg) 95C.

B.P. (0.03 mm. Hg) 98 C.

3.1. 0.01 mm. Hg) C;

3.1. (0.01 mm. Hg) 105-110 C:

B.P. (0.09 mm. Hg) -112" C."

BJP. (0.13 mm. Hg) 120-123 C:

3.1.. (0.05 mm. Hg) 117 C.

B.P. (0.04 mm. Hg) 117118 C;

B.P. 0.05 mm. Hg) 120 0.

B1. (0.08 mm. Hg) C.

HP. (0.3 mm. Hg) 108-110 C.

What is claimed is:

1- A method for combatting harmful insects and acarids which comprisesapplying thereto an insecticidally and acaricidally elfective amount ofa compound of the formula R20 wherein R and R each represents loweralkyl, X represents a member selected from the group consisting ofoxygen and sulfur, R represents a member selected from the groupconsisting of hydrogen, chlorine and lower alkyl, and R represents loweralkoxy.

2. The method according to claim 1 in which the compound is of theformula 3. The method according to claim 1 in which the compound is ofthe formula 01 (CHzO)2POCH=JIUOOC2 5 4. The method according to claim 1in which the compound is of the formula 5. The method according to claim1 in which the compound is of the formula 6. The method according toclaim 1 in which the compound is of the formula 7. The method accordingto claim 1 in which the compound is of the formula 9. The methodaccording to claim 1 in which the compound is of the formula 10. Aninsecticidal and acaricidal preparation comprising a carrier and aninsecticidally and acaricidally effective amount of a compound of theformula R1O\1"{ R:

P0CH=C-R| wherein R and R each represents lower alkyl, X represents amember selected from the group consisting of oxygen and sulfur, Rrepresents a member selected from the group consisting of hydrogen,chlorine and lower alkyl, and R represents lower alkoxy.

References Cited UNITED STATES PATENTS 3,014,839 12/1961 Stiles et al.260-941 X 3,081,220 3/ 196-2 Turner et al. 260-941 X 3,116,201 12/1963Whetstone et al. 260-946 X STANLEY FRIEDMAN, Primary Examiner

